Nitrogen containing cyclic ketone and a process of preparing it



Patented Oct. 17,1933 w f i v UNITED STATES PATE'NT'T'JOFFICE 1 ZNITROGEN CONTAINING CYCLIC KE'lONE l i AND A PROCESS OF PREPARING 1r Heinrich Greune, Wilhelm Eckert, and Heinrich Sieber, Frankfort-on-the-Main-Hochst, and Gerhard Langbein, Hofheim in Taunus, Ger- I many, assignors to General Aniline Works,

Inc., New York, N. Y., a corporation of Dela-v ware- No Drawing. Application October 6, 1930, firiigzglo. 486,862, and in Germany October 11 Claims. (Cl. 260-127) h Present invention relates to nitrogen 'con- Such products obtainable according to the pres-. tainmg cychc ketones and a process of preparing ent ,process as correspond with the. following them. probable iormulai We have found'that nitrogen containing cyclic l l 5 ketones are obtainable by causing a compound of f l i a a 60 the following formula I i I cN .cHi coox a f O= H wherein X stands for hydrogen, an alkali metal a 65 residue or an alkyl group to react with a polynuclear aromatic compound containing at least one pair oi" freeperi-positions in the presence of an a t t a acid condensing agent and, if desired, of an inert wherein the carbon atoms C1, C2 and C3 are memdiluent. The reaction is preferably carried out bers of an aro atic roupin o t e ap a 70 in such a manner that the components are heated 1' anthr c n Se s C1 a C3 representing first at an elevated temperature which is lower bon atoms occupying the peri-positions of said than the decomposition temperature of the cyang up g are to be considered a new productsl acetic acid, as, for instance, at about 70 C. to They are generallyo tained inthe form o their about 140 C. and later on at a higher temperasaltsespecially the. hydr0ch1orides', butrth'e cor- 7 ture, preferably at about 150 C. to about 190 C. responding free imides may easily. be: obtained As acid condensing agents there may be used, for therefrom by aftreatriient with alkali. instance, aluminium chloride, zinc chloride, iron The constitution, of the new cyclic ketones has chloride or the like. As diluents there may be been proved by oxydative degradation;

used inorganic salts as,for instance, sodium chlo- The products obtained according 'to the pres- 0 ride, potassium chloride, sodium fluoride or the ent process are valuable intermediate products like or organic solvents as, for instance, monofor;the preparation of dyestuffs.

chlorobenzene or trichlorobenzene. In many .7 :Thei ollowin examples illustrate the invention, cases it is suitable to add to the'reactionmixtur e but they are not int endedtolimit it thereto:

a substance of a-catalytic action such, for in- (1) .300 parts of sodiumealuminium-chloride stance, as phosphorus oxychloride or to introduce are melted and a mixture of 15 parts ,of. acenaphgaseous hydrochloric acid. By these'additions the thene and l0,,par ts of cyanoacetic acid is added yield of cyclic ketones may be increased and in at C. The temperature risesto' C.- many cases the quantity of the condensing agent C. with evolutionof hydrochloric acid, the whole 36 required for this reaction can be diminished. The is heated to and this temperature is main: 9

cyano-acetic acid may be used as such but also tained for sometime while stirring. in the form of a salt or an ester. After decomposition with ice-water, the whole When using, for instance, acenaphthene and is filtered with suctionandjwashed with a small cyano acetic acid as starting materials, the new quantity of water. ;The. residue is extracted with 40 reaction probably occurs in such amanner. that hot waterlwith addition of a, small quantity of 95 the cyano group is first added to the hydrocar sulfuric acid]; By adding to the filtrateconcenbon and the mono-ke im de 0f the peri-indantrated hydrochloric acid or a solution of sodium dione is then formedwith elimination of water chloride, the condensation product is precipiand alcohol respectively, which reaction may be tated, which crystallizes in small yellow needles,

45 illustrated by the following scheme: 1 melting above 300C. It represents probably the 100 nio 'on +Hooo hydrochloride of the ketimide of the periacenaphthene indandione of the followingformula:

The yield is good. The product dissolves concentrated sulfuric acid to a yellow solution having an intense'green fluorescence. V

When the ketim'ide hydrochloride isdissolved in warm water and -mixed with concentrated caustic soda solution, the free monoketimide of the peri acenaphthene indandione separates in the form of a yellow powder. By recrystallization from alcohol, brilliant. yellowish-brown needles of melting point 285"v C.287 C. are obtained.

(2) 27 parts of phosphorus oxychloride are introduced, drop by drop, at C. into a molten mixture of 255 parts of aluminium chloride, 30 parts of sodium chloride, 21 parts of potassium chloride and 9 parts of sodium fluoride. Thereupon a mixture'of 15 parts of acenaphthene and 10 parts of cyanoacetic acid is added at '7080 C; and the whole is stirred'for 1 hour at 80C. The

temperature is then raised to 160 C. and maintained for one hour.

Afterv decomposition with ice water, the product is worked up as indicated in Example 1. There is obtained with agood yield the hydrochloride of the same mono ketimide of the periacenaphthene indandione as in Example 1;

(3) Dry hydrogen chloride is introduced into a molten mixture of] 127.5 parts 'of aluminium chloride, 15 parts of sodium chloride 105 parts of potassium chloride and 4.5 parts "of sodium fluoride and a mixture of 15 parts of acenaphthene and 10 parts of cyano-acetic acid is added at 80 C. The whole is stirred first for l'hour at 80 C. and then for 5 hours at 160 C. Hydrochloride is introduced in the mixture as long as the reaction lasts. "Thereupon the mixture is poured on ice and the product is worked up as in Example 1. The yield of the hydrochloride of the mono-ketimide' of the peri-acenaphthene indandione thus obtained is gojod;

"1(4) Hydrogen chloride is introduced into a molten mixture as indicated in'Example 3 while the whole is first heated for 5 hours to 80 C. and then for a prolonged time to 110 C.-120 C. The yield of the compound thus obtained is the same as that obtained according to Example 3.

(5) 14.2 parts of a-methyl-naphthalene and 10 parts 'of cyanoacetic acid are introduced at 80 C. into a molten mixture of 255 parts of aluminium chloride, 30 parts of sodium chloride, 21 parts of potassium chloride and 9 parts of sodium fluoride. The whole is stirred at 80C. for hour and heated subsequently to 160 C.- 180 C. for 1 hourj water and fllteredwith suction. The residue is extracted with boiling. dilute sulfuric acid; the ketimide hydrochloride of the a-methyl-perinaphthindandione of the following probable formula: I V 1 is precipitated from the filtrate by addition of a solution of sodium chloride. The product is a yellow powder, which is soluble in hot water. -It dissolves in concentrated sulfuric acid to a 'yellow solution, having an'intense green fluores-;

cence. I The naphthalene-1.4.5tricarboxylic acid is obtained therefrom by oxidation.

(6) A mixture of 18 parts of anthraceneiand 10 parts of cyanoacetic acid is introduced at C. into melted aluminium chloride to which the same: ingredients have been 'addedas indicated in Example 5. The mixture is heatedlfor lhour at 80 C. and subsequently, for .4 hours, at 160. C. After decomposition, the whole is filtered with suction, the residue is extracted .with dilutesul phuric acid and the product is then precipitated from. the filtrate by additionof-asolution of sodium chloride, filtered with suction andjdried. ,A dark redpowder is thusobtained, which 'dis-. solves in water to a redsolution, and inconcentrated sulfuric acid to a bluish-red solution having a yellowish red fluorescence. It probably corresponds with the following formula:

and maintained for several hours. The whole is I then mixed with water, the trichlorobenzene is expelled by means of steam and the residue is filtered with suction. The product is worked up by extraction with dilute sulfuric acid as described in Example 1. -A satisfactory yield is obtained. a (8) Into a melted mixture of 255 parts of aluminium chloride, 80 parts of sodium chloride, 21 parts of potassium chloride and 9 parts of sodium fluoride, there are introduced 30 parts of acenaphthene at a temperature of 80C. and 26 parts of ethyl ester of cyanoacetic acid'aresubsequently added drop by drop- The whole is stirred for V hour at 85 C.'-90 C. and heated to 160 C. for 1 hour. The product is worked up as described in Example 1 and the hydrochloride of the mono-ketimide of the peri-acenaphtheneindandione is obtained ina satisfactory yield. Thereupon the massis decomposed with ice- 1 to 80 C. for hour and then to 160 C. for 1% hours. After decomposition, the mixture is subsequently worked up as described in Example 1, whereby the hydrochloride of the mono-ketimide of the peri-acenaphthene-indandione is obtained in a satisfactory yield.

(10) 30 parts of acenaphthene, v20 parts .of cyanoacetic acid and 150 parts of zinc chloride are thoroughly ground and heated slowly to 160 C., while stirring, whereby a viscous melt is obtained. The above temperature is maintained for 2 hours and the mixture is decomposed with water. The product is worked up as in Example 1 and the hydrochloride of the mono-ketimide is obtained in the form of a yellow crystalline powder.

We claim: 7

1. The process which comprises causing a compound of the following formula:

wherein X stands for hydrogen, and alkali metal or an ethyl group to act first at a temperature of about C. to about 140 C. and then at a temperature of about 150 C. to about 190 C. upon a polynuclear aromatic compound of the acenaphthene, naphthalene and anthracene series containing at least one pair of free peri-positions in the presence of an acid condensing agent.

2. The process which comprises causing a compound of the following formula:

CN-CHzCOOX wherein X stands for hydrogen, an alkali-metal or an ethyl group to act first at a temperature of about 70 C. to about 140 C. and then at a temperature of about 150 C. to about 190 C. upon a polynuclear aromatic compound of the acenaphthene, naphthalene and anthracene series containing at least one pair of free peri-positions in the presence of an acid condensing agent and an inert diluent.

3. The process which comprises causing a compound of the following formula:

wherein X stands for hydrogen, an alkali metal residue or an ethyl group to act first at a temperature of about 70 C. to about 140 C. and

then at a temperature of about 150 C. to about 190C. upon a polynuclear aromatic compound of the group consisting of naphthalene, acenaphthene and anthracene containing at least one pair of free peri-positions in the presence of a metal chloride of acid condensing action.

4. The process which comprises causing a compound of the following formula:

wherein X stands for hydrogen, a sodium metal residue or ethyl, to act first at about 70 C. to about 7 bluish-red solution of yellowish-red fluorescence 140 C. and then at about 150 C. to about 190 C. upon a polynuclear aromatic hydrocarbon of the group consisting of naphthalene, acenaphthene and anthracene containing at least one pair of free peri-positions in the presence of a metal chloride of acid condensing action and an inert diluent.

6. The process which comprises causing cyanacetic acid to act first at about C. and then at about 160 C. upon acenaphthene in the presence of aluminium chloride and dry 'trichlorobenzene.

7. The process which comprises causing cyanacetic acid to act first at about 80 C. and then.

at about 160 C. to about 180 C, upon alphamethylnaphthalene in the presence of aluminium chloride mixed with sodium chloride, potassium chloride and sodium fluoride.

8. The process which comprises causing cyan- .acetic acid to act first at about 80 C. and then at about 160 C. to about 180 C. upon anthracene in the presence of aluminium chloride mixed with sodium chloride, potassium chloride and sodium fluoride.

9. The compound of the following probable formulaz. I

being in the form of its hydrochloride a yellow powder soluble in hot water, which dissolves in concentrated sulfuric acid to a yellow solution of strong green fluorescence and yielding by oxydation the naphthalene 1.4.5-tricarboxylic acid.

10. The compound of the following probable formula:

I =NH Cfi being in the form of its hydrochloridea dark red powderwhich dissolves in warm water to ared solution and in concentrated sulfuric acid to a and yielding by oxidation the'anthracene-l-Q- dicarboxylic acid.

11. The compounds of the general probable formula:

l 1110 Gr- NH I wherein the carbon atoms C1, C2 and Ca aremembers of an aromatic hydrocarbon radical of the group consisting of naphthalene and anthracene radicals, C1 and Ca representing carbon atoms radical.

HEINRICH GREUNE. GERHARD LANGBEIN. WILHELM ECKERT. HEINRICH SIEBER.

occupying the peri-positions of said hydrocarbon. I 

